Compositions containing amino-polyureylene resin

ABSTRACT

COMPOSITIONS COMPRISING A MIXTURE OF AN AMINOPOLYUREYLENE RESIN HAVING A MOLECULAR WEIGHT IN THE RANGE OF ABOUT 300 TO 100,000 AND AN ACTIVE MATERIAL SELECTED FROM THE GROUP OF ANTIBACTERIAL MATERIALS, TARNISH INHIBITORS, ULTRA VIOLET ABSORBERS, FLUOROSCENT BRIGHTENERS, BLUING AGENTS AND SKIN TREATING MATERIALS, THE WEIGHT RATIO OF RESIN TO ACTIVE MATERIAL BEING EFFECTIVE TO IMPROVE THE PROPERTIES OF THE ACTIVE MATERIAL AND BEING SELECTED FROM THE RANGE OF 1:1 TO 20:1. PREFERRED COMPOSITIONS COMPRISE 2% TO 99% BY WEIGHT OF A WATER-SOLUBLE ORGANIC DETERGENT, .05% TO 5% BY WEIGHT OF AMINOPOLYUREYLENE RESIN AND 0.05 TO 5% BY WEIGHT OF ACTIVE MATERIAL.

3,726,815 COMPOSITIONS CONTAINING AMINO- POLYUREYLENE RESIN Paul SheldonGrand, South Bound Brook, N.J., assiguor to Colgate-Palmolive Company,New York, N.Y. N Drawing. Filed Nov. 16, 1970, Ser. No. 90,154

U.S. Cl. 252-544 7 Claims ABSTRACT OF THE DISCLOSURE Compositionscomprising a mixture of an aminopolyureylene resin having a molecularweight in the range of about 300 to 100,000 and an active materialselected from the group of antibacterial materials, tarnish inhibitors,ultra violet absorbers, fluorescent brighteners, bluing agents and skintreating materials, the weight ratio of resin to active material beingeffective to improve the properties of the active material and beingselected from the range of 1:1 to 20:1. Preferred compositions comprise2% to 99% by weight of a water-soluble organic detergent, .05 to 5% byWeight of aminopolyureylene resin and 0.05 to 5% by weight of activematerial.

The invention relates to improved compositions comprising awater-soluble and/or water-insoluble active material having the capacityto impart a residual characteristic to surfaces treated therewith suchas antibacterial compounds, tarnish inhibitors, ultra-violet absorbers,fluorescent brighteners, bluing agents and skin treating materials andan aminopolyureylene (APU) resin in an amount effective to enhance theeffects of the active materials. The APU resins appear to enhance thedeposition and/or retention of the water-soluble and water-insolubleactive substances on the surfaces contacted therewith.

The capacity of the APU resin to improve the effectiveness of the activematerials on surfaces contacted therewith surprisingly is maintained inthe presence of watersoluble organic detergents and, therefore,detergent compositions containing the mixture of active material and APUresin represent preferred embodiments. Such detergent compositionsinclude dishwashing detergents, shampoos, laundry detergents,hard-surface cleaners and toilet bars. The effectiveness of the APUresins in the presence of minor and major amounts of water-solubleorganic detergents is surprising because the effectiveness of the activematerials is due to the deposition and/or retention of the activematerials on surfaces contacted therewith and detergents normally tendto minimize deposition and retention of such materials on the washedsurfaces. Thus, usually only a small percentage of the active materialsin a detergent composition is actually retained on a particular surfaceor substrate after washing and, optionally, rinsing. Accordingly, toachieve a particular level of activity, the concentrations of activematerial must be increasedwith an attendant increase in costwhen used asa component in a detergent composition.

While the mechanism by which the improved effects are obtained is notunderstood, it appears that the APU resin may unite either with theactive material or the contacted surface to increase the affinity of theactive material for the surface. In many cases, an increase in theWeight of active material retained by the surface has beenquantitatively verified. However, no absolute mechanism has been definedand the invention is not limited to any particular theory.

Generally, the improved compositions of this invention consistessentially of a mixture of an aminopolyureylene resin having amolecular weight in the range of about 300 to 100,000 and awater-soluble or waterinsoluble active material having the capacity toimpart a 3,725,815 Patented Apr. 10, 1973 residual property to surfacestreated therewith and selected from the group consisting of (A)antibacterial compounds, (B) tarnish inhibitors, (C) ultra-violetabsorbers, (D) optical brighteners, (E) bluing agents and (F)skin-treating compounds, the weight ratio of resin to active materialbeing effective to improve the effects of the active material andselected from the range of 1:1 to 20:1 preferably 1:1 to 5:1. Preferredcompositions are detergent compositions comprising 2% to 99% by weightof a water-soluble, organic detergent, 0.05% to 5% by Weight ofaminopolyureylene resin and about 0.05 to 5% by weight of activematerial.

Also, within the scope of the invention is a method for improving theeffectiveness of active materials on surfaces contacted therewith whichcomprises contacting the surface with a water solution or dispersion ofthe active material and an effective amount of the aminopolyureyleneresin sufficient to improve the effect of the active material retainedon the treated surface after the contacting solution is removed.

The APU resins suitable for use in the described compositions and methodhave a molecular weight in the range of about 300 to 100,000 and arecharacterized by the following repeating unit:

YisOorS,andnis2or3.

Such APU resins and their cosmetic effectiveness are set forth in thecopending application of Paul Grand entitled Cosmetic Compositions filedof even date herewith.

Thus, suitable A-PU resins include both the polyureaand thepolythiourea-containing compounds. Preferred APU resins have a repeatingunit where Y is oxygen, n is 3, and X is selected from the groupconsisting of N-C alkyl and Generally, the number of repeating units inthe resin will be sufficient to yield a polymer having a molecularweight in the range of about 300 to 100,000. Preferred APU resins havean average molecular weight in the range of 1,000 to 20,000 and aparticularly preferred resin is the reaction product of equimolarquantities of N-methyl, bis(3-amino-propyl) amine and urea having amolecular weight of about 4,300.

The molecular weight of the APU resins is based upon aqueous gelpermeation chromatographic analysis. The separation is carried out inoxalic acid solution, adjusted to pH 3.5, on three Corningcontrolled-pore glass columns (nominal pore sizes 175, 125 and A.) inseries. Detec tion is by differential refractometer. Reference compoundsare dextran polysaccharides of molecular weights of 150,- 000, 110,000,40,000, 20,000 and 10,000 and sucrose and galactose.

The APU resins which can be used in the compositions of this inventionare prepared by reacting, for example, 145 grams of N-methylbis(3-aminopropyl) amine (1.0 mole) and 60 grams of urea (1.0 mole) in a3-necked flask equipped with a thermometer, mechanical stirrer,condenser, and nitrogen sparge tube. Nitrogen is bubbled slowly throughthe solution throughout the course of the reaction. The solution isheated to 140 C. over a 20- minute interval where ammonia begins toevolve. The solution is further heated to 250 C. over a 30 minuteinterval and allowed to cool. The product is a hard, resinous powder(Resin A) having a molecular weight of about 4,800. The secondary amineanalogues can be made by the above process if bis(3-aminopropyl) amineor bis(2-arninoethyl) amine are reacted with urea or thiourea. Thepiperazine analogues are made by reacting N,N-di(3-aminopropyl)piperazine or N,N'-di(2-aminoethyl) piperazine with urea or thiourea.The N-C to C alkyl analogues are prepared by reacting N-C to C alkylbis(3-aminopropyl) amine or N-C to C alkyl bis(2- aminoethyl) amine withurea or thiourea. Additional analogues are prepared by the followingreactions:

$113 Rosin A epichlorohydrin IIH CH2CHCH2CI analogues CH3 II+ analogues-l- NaOH (kHz-CHCHzCI 6H CH HzCH-CH: analogues CH CH3 1 1 analogues H2Ol l )H2CH---CHz HzCH-CHzOH analogues CH Resin A dimethyl sulfate l I+analogues The preparation of the remaining analogues is well within theskill of the art following the above techniques.

The active materials which are potentiated by the APU resin are wellknown and have been used for treating surfaces and substrates to impartcertain residual characteristics to the contacted surfaces. The treatedsurfaces or substrates include proteinaceous materials such as hair andskin, textiles such as cotton, rayon and synthetic fibers, andporcelain, wood, plastic and metal. Such active materials may bewater-soluble such as cetyl dimethyl benzyl ammonium bromide and gelatinor water-insoluble such as zinc Z-pyridinethiol-l-oxide and opticalbrighteners. To facilitate activity and utility, the water-insolublematerials are usually in the form of finely divided particles having adiameter in the range of about 0.5 to 50 microns. Suitable activematerials include antibacterial compounds, tarnish inhibitors,ultra-violet absorbers, optical brighteners, bluing agents and skintreating materials The zinc and sodium salts of 2-pyridinethiol-1-oxideare particularly preferred.

Other suitable antibacterial compounds are the substituted bisphenolshaving the formula wherein X is a halogen such as chlorine or bromine, nis 1-3 and R is an alkylene of 14 carbon atoms or divalent sulfur.Typical compounds include bis(3,5,6-trichloro-2- hydroxyphenyl) methaneor sulfide, bis(5-chloro-2-hydroXyphenyDmethane and bis(3,5dichloro-2-hydroxyphenyl)methane or sulfide.

Suitable antibacterial substituted salicylanilides have the structureformula wherein Y is hydrogen, halogen, or trifiuoromethyl and Z ishydrogen or halogen. Among the suitable salicylanilides are3,4,5-tribromosalicylanilide; 5-bromosalicyl-3,5-di-(trifiuoromethyl)anilide; 5-chlorosalicyl 3,5-di(trifluoromethyDanilide;3,5-dichlorosalicyl 3,4 dichloroanilide; and 5-chlorosalicyl 3trifiuoromethyl-4-chloroanilide. These and other useful salicylanilidesare disclosed in US. patent specification No. 2,703,332.

Satisfactory substituted carbanilides have the following generalstructure wherein Y is hydrogen, halogen, or trifiuoromethyl, W ishalogen or ethoxy, and W is hydrogen or halogen. Included among thesuitable carbanilides are 3,4,4-trichlorocarbanilide;4,4-trifluoromethyl-3,4,4-trichlorocar banilide; 3,3bis(trifiuoromethyl-4-ethoXy-4'-ehlorocarbanilide; and 3,5bis(trifluoromethyl) 4'-chlorocarbanilide.

Other antibacterial materials are the mono-higher-alkyl quaternaryammonium salts having the following structural formula:

[R 1-E-R3] A 4 wherein R is C to C alkyl, R and R are each C -C alkyl,RA, is C C alkyl or benzyl and A is an anion selected from the groupconsisting of chlorine, bromine, iodine, and methosulfate. A preferredcompound is cetyl trimethyl ammonium bromide.

Additional useful antimicrobial compounds include 5,7- diiodo 8 hydroxyquinoline, 1,6-di(4'-chlorophenyldiiguanado) hexane, andS-chloro-Z(2,4-dichlorophenoxy)phenol, C to C isoquinolinium halides,such as lauryl isoquinolinium bromide, and C -C alkyl pyridinium halide.

The tarnish inhibitors potentiated by APU resins include, for example,benzotriazole and ethylenethiourea.

Ultraviolet absorbers potentiated by APU resins have the structuralformula where X, Y, and Z are selected from the group consisting ofhydrogen, hydroxy, C to C alkoxy and carboxy, at least one of said X, Y,and Z being oxy. Preferred compounds include2-hydroxy-4-n-octoxy-benzophenone and2-hydroxy-4-methoxy-2'-carboxy-benzophenone.

The optical or fluorescent brightener active materials which arepotentiated by the APU resins are selected from the group consisting ofstilbene disulfonates, quaternized aminoalkyl substituted phenylsulfonamides of aryl pyrazolines, substituted styrylnaphth oxazoles, andsubstituted aminocumarins.

Suitable stilbene disulfonate fluorescent brighteners have the formulawherein X is OH,

Suitable compounds are disodium 4,4 bis [4-anilino-6-methoxyanilino-s-triazin-Z-yl amino] 2,2 stilbene disulfonate anddisodium 4, 4'-bis(4,-6-dianilino-s-triazin-2-ylamino)-2,2'stilbene-disulfonate.

Suitable quaternized aminoalkyl substituted phenyl sulfonamides of arylpyrazoline have the following formula:

Wherein X is hydrogen, phenyl, or halogenated phenyl with not more thanone X being hydrogen and Y is a quaternized Q-somnnnma (R2) wherein R isC -C alkyl and R and R are each selected from the group consisting ofhydrogen and C C alkyl. A typical compound is quaternized-1-p(sulfonyl-'-dimethyl aminopropyl amido)-phenyl-3-p-chlorophenyl pyrazoline.

Suitable oxazole fluorescent brighteners have the structural formula:

Rm qgwacagi wherein A and B are different and represent oxygen andnitrogen, and R represents individually hydrogen, alkyl groups having 1to 6 carbon atoms, chlorine or fluorine. A preferred oxazole brighteneris 2-strylnaphth (1,2-d) oxazole.

Additional fluorescent brighteners potentiated by APU resin are thewater-soluble substituted aminocoumarins having the following structuralformula:

wherein R is hydrogen or C -C alkyl. A preferred compound is 4 methyl, 7dimethyl amino coumarin.

A bluing material which is potentiated by APU resin is ultramarine blue.This is a well-known blue pigment occurring naturally as mineral thelapis lazuli. It can be made, for example, by igniting a mixture ofkaolin, sodium carbonate or sulfate, sulfur, and carbon. It is insolublein water and is stable when in contact with bleaching agents, alkali,and light. Details for synthetic ultramarines are given in the textUltramarines, Their History and Characteristics, Reckitts (Colours)Ltd., Hull, England. Preferred are micropulverized, syntheticultramarine blues, particularly grades RS4RS8 provided by Reckitts. Thepigment is in the form of particles substantially all of which exhibit adiameter of less than about 0.05 millimeter, and is characterized by theability to impart a faint blue visible shade to fabrics treatedtherewith without staining such fabrics when used at recommendedconcentration and fashion, being generally considered to benon-substantive, or at least non-accumulative, on fabrics.

The skin-treating materials which are enhanced by the APU resins are thewater-soluble, substantive proteins. Such proteins are substantive tothe hair and skin in the presence of detergents. Suitable proteins arewatersoluble polypeptides, having a molecular weight in the range ofabout (amino acid) to about 20,000, preferably from about 800 to 12,000.Such polypeptides are obtained by hydrolysis of protein materials suchas hides, gelatin, collagen, and the like, with collagen protein beingpreferred, using well-known processes. During hydrolysis the proteinmaterials are gradually broken down into their constituent polypeptidesand amino acids by prolonged heating with acids, e.g., sulfuric acid, oralkalis, e.g., sodium hydroxide, or treatment with enzymes, e.g.,peptidases. First, high molecular weight polypeptides are formed, and ashydrolysis proceeds these are converted progressively to simpler andsimpler polypeptides, to tripeptides, I

depeptides and finally to amino acids. It is obvious that thepolypeptides derived from proteins are complex mixtures. The preferredhydrolysates are obtained from boneor skin-derived collagen protein byenzymatic hydrolysis and are sold under the trade names WSP-X-250 andWSP-X-lOOO of Wilson Pharmaceutical and Chemical Corporation.

Other skin-treating materials whose skin-slip or antifriction propertiesare enhanced by APU resins include ethylene oxide polymers having a.molecular weight in the range of about 500,000 to 4,000,000 which aresold under the trade name Polyox.

The water-soluble organic detergent materials which can be used informing the preferred detergent compositions of this invention may beselected from the group consisting of anionic, nonionic, amphoteric,zwitterionic, polar nonionic, and cationic detergents, and mixtures oftwo or more of the foregoing detergents.

The anionic surface-active agents include those surfaceactive ordetergent compounds which contain an organic hydrophobic groupcontaining generally 8 to 26 carbon atoms and preferably 10 to 18 carbonatoms in their molecular structure, and at least one water-solubilizinggroup selected from the group of sulfonate, sulfate, carboxylate,phosphonate and phosphate so as to form a water-soluble detergent.

Examples of suitable anionic detergents which fall within the scope ofthe anionic detergent class include the water-soluble salts, forexample, the sodium, ammonium, and alkylammonium salts, of higher fattyacids or resin salts containing about 8 to 20 carbon atoms, preferably10 to 18 carbon atoms. Suitable fatty acids can be ob tained from oilsand waxes of animal or vegetable origin, for example, tallow, grease,coconut oil, tall oil and mixtures thereof. Particularly useful are thesodium and potassium salts of the fatty acid mixtures derived fromcoconut oil and tallow, for example, sodium coconut soap and potassiumtallow soap.

The anionic class of detergents also include the watersoluble sulfatedand sulfonated synthetic detergents having an alkyl radical of 8 to 26,and preferably about 12 to 22 carbon atoms. (The term alkyl includes thealkyl portion of the higher acyl radicals.)

Examples of the sulfonated anionic detergents are the higher alkylmononuclear aromatic sulfonates such as the higher alkyl benzenesulfonates containing from 10 to 16 carbon atoms in the higher alkylgroup in a straight or branched chain, for example, the sodium,potassium, and ammonium salts of higher alkyl benzene sulfonates,

higher alkyl toluene sulfonates, higher alkyl phenol sulfonates andhigher naphthalene sulfonates. A preferred sulfonate is linear alkylbenzene sulfonate having a high content of 3- (or higher) phenyl isomersand a correspondingly low content (well below 50%) of 2- (or lower)phenyl isomers, that is, wherein the benzene ring is preferably attachedin large part at the 3 or higher (for example, 4, 5, 6 or 7) position ofthe alkyl group and the content of the isomers in which the benzene ringis attached in the 2 or 1 position is correspondingly low. Particularlypreferred materials are set forth in US. Pat. 3,320,174.

Other suitable anionic detergents are the olefin sulfonates, includinglong-chain alkene sulfonates, long-chain hydroxyalkane sulfonates ormixtures of alkene sulfonates and hydroxylalkane sulfonates. Theseolefin sulfonate detergents may be prepared in a known manner by the reaction of S with long-chain olefins containing 8 to 25', preferably 12to 21 carbon atoms and having the formula RCH=CHR where R is a higheralkyl group of 6 to 23 carbons and R is an alkyl group of 1 to 17carbons or hydrogen to form a mixture of sultones and alkene sulfonicacids which is then treated to convert the sultones to sulfonates. Otherexamples of sulfate or sulfonate detergents are paraffin sulfonatescontaining about to 20 and preferably about 15 to 20 carbon atoms, forexample; the primary paraffin sulfonates are made by reacting longchainalpha olefins and bisulfites and parafiin sulfonates having thesulfonated group distributed along the paraffin chain as shown in US.Pats. 2,503,280; 2,507,088; 3,260,- 741; 3,372,188; and German .Pat.735,096; sodium and potassium sulfates of higher alcohols containing 8to 18 carbon atoms such as sodium lauryl sulfate and sodium tallowalcohol sulfate; sodium and potassium salts of a-sulfofatty acid esterscontaining about 10 to 20 carbon atoms in the acyl group, for example,methyl ws ulfomyristate and methyl OL-SlllfOtfillOWfltC, ammoniumsulfates of monoor di-glycerides of higher (C -C fatty acids, forexample, stearic monoglyceride monosulfate; sodium and alkylolammoniumsalts of alkyl polyethenoxy ether sulfates produced by condensing 1 to 5moles of ethylene oxide with one mole of higher (Cg-C1 alcohol; sodiumhigher alkyl (C -C glyceryl ether sulfonates; and so dium or potassiumalkyl phenol polyethenoxy ether sulfates with about 1 to 6 oxyethylenegroups per molecule and in which the alkyl radicals contain about 8 toabout 12 carbon atoms.

The suitable anionic detergents include also the C to C acylsarcosinates (for example, sodium lauroyl sarcosinate), sodium andpotassium salts of the reaction product of higher fatty acids containing8 to 18 carbon atoms in the molecule esterified with isethionic acid,and sodium and potassium salts of the C to C acyl N-methyl taurides, forexample, sodium cocoyl methyl taurate and potassium stearoyl methyltaurate.

Anionic phosphate surfactants in which the anionic solubilizing groupattached to the hydrophobic group is an oxyacid of phosphorous are alsouseful in the detergent compositions. Suitable phosphate surfactants arethe sodium, potassium, and ammonium alkyl phosphate esters such as (RO)PO M and ROPO M in which R represents an alkyl chain containing fromabout 8 to 20 carbon atoms or an alkyl phenyl group having 8 to 20carbon atoms and M represents a soluble cation. The compounds formed byincluding about 1 to 40 moles of ethylene oxide in the foregoing esters,for example,

are also satisfactory.

The particular anionic detergent salt will be suitably selected,depending upon the particular formulation and the proportions therein.Suitable salts include the ammonium, substituted ammonium (mono-, di-,and triethanolammonium), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts. Preferredsalts are the ammonium, triethanolammonium, sodium, and potassium saltsof the higher alkyl sulfates and the C to C acyl sarcosinates.

The nonionic synthetic organic detergents are generally the condensationproduct of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxy, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideor with the polyhydration product thereof, polyethylene glycol, to forma nonionic detergent. Fnrther, the length of the polyetheneoxy chain canbe adjusted to achieve the desired balance between the hydrophobic andhydrophilic elements.

The nonionic detergents include the polyethylene oxide condensate of onemole of alkyl phenol containing from about 6 to 12 carbon atoms in astraightor branchedchain configuration with about 5 to 30 moles ofethylene oxide, for example, nonyl phenol condensed with 9 moles ofethylene oxide, dodecyl phenol condensed with 15 moles of ethylene anddinonyl phenol condensed with 15 moles of ethylene oxide. Condensationproducts of the corresponding alkyl thiophenols with 5 to 30 moles ofethylene oxide are also suitable.

Still other suitable nonionics are the polyoxyethylene polyoxypropyleneadducts of l-butanol. The hydrophobe of these anionics has a minimummolecular weight of 1,000 and consists of an aliphatic monohydricalcohol containing from 1 to 8 carbon atoms to which is attached aheteric chain of oxyethylene and oxypropylene. The weight ratio ofoxypropylene to oxyethylene covers the range of 95 to 85:15. Attached tothis is the hydrophilic polyoxyethylene chain which is from 44.4 to 54.6of the total molecular weight.

Also included in the nonionic detergent class are the condensationproducts of a higher alcohol containing about 8 to 18 carbon atoms in astraight or branchedchain configuration condensed with about 5 to 30moles of ethylene oxide. For example, lauryl-myristyl alcohol condensedwith about 16 moles of ethylene oxide.

A particularly useful group of nonionics is marketed under the tradename Pluronics. The compounds are formed by condensing ethylene oxidewith a hydrophobic base formed by the condensation of propylene oxidewith propylene glycol. The molecular weight of the hydrophobic portionof the molecule is of the order of 950 to 4,000 and preferably 1,200 to2,500. The addition of polyoxyethylene radicals to the hydrophobicportion tends to increase the solubility of the molecule as a whole. Themolecular weight of the block polymers varies from 1,000 to 15,000, andthe polyethylene oxide content may comprise 20% to 80% by weight.

Zwitterionic detergents such as the betaines and sulfobetaines havingthe following formula are also useful:

wherein R is an alkyl group containing about 8 to 18 carbon atoms, R andR are each an alkylene or hydroxyalkylene group containing about 1 to 4carbon atoms, R; is an alkylene or hydroxyalkylene group containing 1 to4 carbon atoms, and X is C or SrO. The alkyl group can contain one ormore intermediate linkages such as amido, ether, or polyether linkagesor nonfunctional substituents such as hydroxyl or halogen which do notsubstantially aifect the hydrophobic character of the group.

When X is C, the detergent is called a betaine; and when X is 5:0, thedetergent is called a sulfobetaine or sultaine. Preferred betaine andsulfobetaine detergents are 1- (lauryl dimethylammonio) acetatel-(myristyl dimethylammonio) propane-3-sulfonate, andl-(myristyldimethyl ammonio)-2-hydroxy-propane-3-sulfonate.

The polar nonionic detergents are those in which the hydrophilic groupcontains a semi-polar bond directly between two atoms, for example, N O,P O, As O, and S- O. There is charge separation between the two directlybonded atoms, but the detergent molecule bears no net charge and doesnot dissociate into ions.

The polar nonionic detergents of this invention include open-chainaliphatic amine oxides of the general formula R R R N O. For the purposeof this invention R is an alkyl, alkenyl, or monohydroxyalkyl radicalhaving about to 16 carbon atoms, R and R are each selected from thegroup consisting of methyl, ethyl, propyl, ethanol, and propanolradicals.

Other operable polar nonionic detergents are the openchain aliphaticphosphine oxides having the general formula 'R R R P O wherein R is analkyl, alkenyl, or monohydroxyalkyl radical ranging in chain length from10 to 18 carbon atoms, and R and R are each alkyl and monohydroxyalkylradicals containing from 1 to 3 carbon atoms.

Examples of suitable ampholytic detergents include the alkylbeta-aminopropionates, RN(H)C H COOM; the alkyl beta-iminodipropionates,RN(C H COOM) the alkyl and hydroxy alkyl taurinates,

and the long-chain imidazole derivatives having the fol lowing formulas:

RzCOOM wherein R is an acyclic group of about 7 to 17 carbon atoms, W isselected from the group of R OH, R COOM, and R OR COOM, Y is selectedfrom the group consisting of -OH-, R OSO R is an alkylene orhydroxyalkylene group containing 1 to 4 carbon atoms, R, is selectedfrom the group consisting of alkyl, alkyl aryl and fatty acyl glyceridegroups having 6 to 18 carbon atoms in the alkyl or an acyl group; and Mis a Watersoluble cation, for example, sodium, potassium, ammonium, foralkylolammonium.

Formula I detergents are disclosed in volume II of Surface Active Agentsand Detergents and Formula II detergents are described in U.S.2,773,068; U.S. 2,781,354; and U.S. 2,781,357. The acyclic groups may bederived from coconut oil fatty acids (a mixture of fatty acidscontaining 8 to 18 carbon atoms), lauric fatty acid, and oleic fattyacid, and the preferred groups are 0; to C alkyl groups. Preferreddetergents are sodium N-lauryl beta-aminopropionate, disodium N-lauryliminodipropionate, and the disodium salt of 2-lauryl-cycloimidium-1-hydroxyl, l-ethoxyethanoic acid, l-ethanoic acid.

Cationic surface active agents may also be employed. Such agents arethose surface active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

Examples of suitable synthetic cationic detergents are normal primaryamines RNH wherein R is C to C the diamines such as those of the typeRNHC H NH wherein R is an alkyl group of about 12 to 22 carbon atoms,such as N-2-aminoethyl stearyl amine and N-2- aminoethyl myristyl amine;amide-linked amines such as those of the type R CONHC H NH wherein R isan alkyl group of 8 to 20 carbon atoms, such as N-Z-amino ethylstearylamide and N-amino ethylmyristyl amide; quaternary ammonium compoundswherein typically one of the groups linked to the nitrogen atom is analkyl group of about 8 to 22 carbon atoms and three of the groups linkedto the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms,including alkyl groups bearing inert substituents, such as phenylgroups, and there is present an anion such as halogen, acetate,methosulfate, etc. The alkyl group may contain intermediate linkagessuch as amide which do not substantially affect the hydrophobiccharacter of the group, for example, stearyl amido propyl quaternaryammonium chloride. Typical quaternary ammonium detergents areethyl-dimethylstearyl ammonium chloride, ben7,yl-dimethyl-stearylammonium chloride, trimethyl-stearyl ammonium chloride, trimethyl-cetylammonium bromide, dimethyl-ethyl-lauryl ammonium chloride,dimethyl-propyl-myristyl ammonium chloride, and the correspondingmethosulfates and acetates.

Preferred detergent compositions of this invention are the liquid,antimicrobial shampoo compositions suitable for washing the hair andscalp. Such compositions consist essentially of about 10% to by weightof a detergent selected from the group consisting of non-soap anionic,amphoteric, and zwitterionic detergents from 0.1% to 3% by weight ofwater-soluble or water-insoluble particulate antimicrobial activematerial, 0.5% to 3.5% of aminopolyureylene resin, and the balanceprimarily water. The shampoo compositions may also include minor amountsof ethanol or isopropanol perfume, color, stearate opacifying agents,ethylene diamine tetracetate or citrate sequestering agents, thickeningagents, and fatty acid alkylolarnide foam boosters.

Other detergent compositions falling within the scope of the inventionare the heavy-duty laundering compositions containing APU polymers andat least one of the active materials potentiated by thepolaminopolyureylene resins, such as antibacterials, fluorescentbrighteners, and bluing agents. Such compositions generally consistessentially of about 8% to 40% by weight of non-soap anionic or nonionicdetergent, about 0.1% to 3% by weight of active material, about 0.5% to3.5 by weight of APU resin and the balance water-soluble inorganic ororganic builder salt. Suitable builders include sodium sulfate, sodiumcarbonate, and sodium nitrilotriacetate as well as the correspondingpotassium compounds. Other compositions are sodiumcarboxymethylcellulose, polyvinylalcohol, perfume, color, etc.

The foregoing laundering detergents may also be prepared in liquid form.Suitable liquids consist essentially of about to by weight of non-soapanionic or nonionic detergent, 10% to by weight of potassiumpyrophosphate, sodium silicate or sodium nitrilotriacetate, 4% to 12% byweight of sodium or potassium xylene or toluenesulfonate, 0.1% to 3.0%by weight of active material, 0.5% to 3.5% by weight of APU resin, andthe balance primarily water. Suitable additives which may be added aresodium carboxymethylcellulose, thickeners, color, and perfume.

In bar form, the detergent material may be soap, anionic, amphoteric,nonionic or mixtures of the foregoing detergents. In addition to theusual proportions of APU resin and active material, the bars may includecolor, perfume, free fatty acids, sodium chloride, and fatty acidalkanolamide suds builders.

Each of the foregoing detergent compositions can be prepared by methodswell known in the art. For example shampoos and built liquid detergentsare prepared by mixing, and particulate laundering detergents areprepared by mixing, chemical drying or spray drying.

The ability of the APU resins to potentiate the deposition of thewater-insoluble materials which function an antibacterial agents ontoproteinaceous substrates, such as hair and skin, is demonstrated in thefollowing radioactive substantivity test. Substantivity is determined bystirring a =1.27-centimeter diameter circular gelatin disk weighingabout milligrams for about five minutes in 10 grams of an aqueous mediumcontaining a known concentration of radioactive tagged material such aszinc Z-pyridinethiol-l-oxide, rinsing the disk five times in 10milliliters of water, drying, and measuring the radiation emission withthe aid of a radiation detector. The absolute degree of deposition ofthe material is determined by comparing the observed counts with thecounts emitted by a known weight of the radioactive material. The effectof APU resin on deposition can be readily ascertained by repeating thetest with a known weight of APU present. Similarly, the effect ofdetergents can be quantitatively measured by including detergents in thetest composition.

The following examples are illustrative of the compositions fallingwithin the scope of this invention.

EXAMPLE 1 An aqueous dispersion of zinc 2-pyridinethiol-1-oxide isprepared by dispersing 0.04 gram of radioactive zinc 2-pyridinethiol-l-oxide containing zinc in one gram of water. Theresultant aqueous dispersion is diluted with 8.96 grams of water withagitation, and the substantivity of the diluted dispersion is determinedusing the foregoing substantivity procedure. The results of theevaluation indicate 40.9 micrograms of zinc-2-pyridinethiol-l-oxide aredeposited on the disk from the aqueous mixture containing 0.4% by weightof the Z-pyridinethiol-l-oxide. When the foregoing experiment isrepeated in the presence of an amino polyureylene resin (Resin A) havinga molecular weight of about 4,300 and the repeating unit 122 microgramsof zinc 2-pyridinethiol-1-oxide are deposited on the disk at aconcentration of 0.5% of said resin in the aqueous test dispersion.Thus, the presence of 0.5 of APU resin results in a 200% increase in thedeposition of zinc-2-pyridinethiol-l-oxide from an aqueous medium.

Use of a resin having a molecular weight of about 5,600 andN,N'-di(3-aminopropyl) piperazine as the repeating unit in the foregoingtest yields comparable results.

EXAMPLE 2 When the procedure of Example 1 is repeated using an aqueoussolution of 0.25% by weight of radioactive (C-l4) cetyltrimethylammonium bromide (CTAB) at pH 4.5 as the test medium, 294micrograms of CTAB are deposited on the gelatin disk. Repetition of thistest in the presence of 0.75% by weight of the APU resin used in Example1 results in the deposition of 679 micrograms of CTAB, an increase indeposition of about When the pH of the test solution is increased to8.5, a deposition of 259 micrograms of CTAB is obtained in the absenceof APU resin and a deposition of 734 micrograms is obtained in thepresence of 3% by weight of the APU resin of Example 1. Thus, a increasein deposition of CTAB is noted at pH 8.5.

EXAMPLE 3 Example 2 is repeated with the exception that a 10% aqueousethanol mixture is substituted for water in the test solution and the pHis adjusted to 6.5. A deposition value of 202 micrograms of CTAB isnoted in the absence of APU resin, and a deposition value of 643micrograms of CTAB is noted in the presence of 0.75 by weight of the APUresin of Example 1. This represents an increase in deposition of about220%. For comparison, only 227 micrograms of CTAB are deposited when theconcen tration of CTAB in the test solution is increased to 1% byweight. Thus, the APU resin is significantly more effective in enhancingdeposition than an increase in the CTAB concentration from 0.25% to 1%,a 300% increase.

EXAMPLE 4 When the procedure of Example 1 is repeated using a0.5%-by-weight aqueous alcoholic (70%) dispersion of radioactive (C-14)bis(3,5,6-trichloro-2-hydroxyphenyl) methane as the test solution, theradioactivity of the gelatin disk averages 2,100 counts per minute(C.P.M.). Repetition of the test in the presence of 1.25% concentrationof the APU resin of Example 1 results in an average radioactivity of13,200 c.p.m. Thus, the presence of the APU resin increases thedeposition of the antimicrobial compound by about 500%. Substantiallysimilar results are noted when either lamb skin or human callus tissueis substituted for the gelatin disk in the foregoing experiment.

The APU resin of Example 1 can be replaced by either a resin having amolecular weight of about 4,600 and the repeating unit or a resin havinga molecular weight of about 6,700 and the repeating unit withsubstantially similar results. Similarly, the substituted methane may besubstituted with 5-chloro-2(2,4- dichlorophenoxy) phenol withsubstantially similar results.

EXAMPLE 5 Tests of the following shampoo illustrate the improved effectsattributable to the APU resin. This shampoo is effective to inhibit thegrowth of Pityrosporum Ovale.

Percent by weight 1 Aminopolyureylene resin having a molecular weight ofabout 4,300 and a repeating unit of When the foregoing composition isformulated with a radioactive zinc 2-pyridinethiol-l-oxide (Zn 65)material and is evaluated using the substantivity procedures of Example1, 20.8 micrograms of radioactive zinc 2-pyridinethiol-l-oxide are notedon the gelatin disk. In this evaluation, 2.5 grams of shampoo arediluted with 7.5 grams of water to simulate normal use dilution ofshampoos, and the diluted shampoo is test solution. Under suchconditions, the concentration of zinc Z-pyridinethiol-l-oxide in thetest solution is 0.4% by weight, and the concentration of APU resin is0.5% by weight. Repetition of the foregoing test with an identicalcomposition not containing APU resin results in the deposition of 8.7micrograms of zinc 2-pyridinethiol-1-oxide. Thus, use of APU resin incombination with zinc 2-pyridinethiol-1- oxide in the presence ofdetergents results in an increase in deposition of about 140%.

To confirm that increased deposition results in enhanced residualactivity, radioactive disks obtained using the foregoing evaluationtechnique are plated in a standard agar medium inoculated with P. ovale,and the diameters of the zone of inhibition are measured aftertwenty-four hours of incubation. These results are shown in Table Itogether with results of non-radioactive disks. Resin A alone has nozone of inhibition.

TABLE I Zone of inhibition after 24 hours (mm.)

Zine Z-pyridinethiol-l-oxide Radioactive Do Nongadioactive.

TABLE II Zone of inhibition (mm.)

One Wo Three APU resin incubation ineubations incubations No 24. 9 5.8 0Yes 43. 5 2A. 5 9. 4

These results indicate that the presence of APU resin results inimproved antimicrobial effectiveness of thezinc-2-pyridinetl'iiol-1-oxide and longer-lasting effectiveness.

EXAMPLE 6 Example 5 is repeated with the exception that theconcentration of zinc 2-pyridinethiol-1-oxide in the shampoo is reducedto 0.4%. 17.4 micrograms of zinc Z-pyridinethiol-l-oxide are depositedon the disk. In the absence of the 2% of APU resin, 6.1 micrograms ofzinc 2-pyridinethiol-l-oxide are deposited on the disk. Again, APU resinsignificantly enhances the deposit of zinc 2-pyridinethiol-l-oxide on aproteinaceous substrate.

EXAMPLE 7 The following liquid detergent composition is an effectiveantimicrobial detergent.

Percent by weight Sodium lauryl triethenoxy ether sulfate 8.0 Lauryldimethyl amine oxide 7.5 Sodium Z-pyridinethiol-l-oxide 2.0 Resin A 1.0Water Balance EXAMPLE 8 Another antimicrobial liquid detergentcomposition having a pH of 8.2 follows.

Percent by weight Cocoamidopropyl dimethyl betaine 1 22.4

Sodium N-(2 hydroxyhexadecyl) methyl taurate 6.0 Sodium hexylbenzenesulfonate 0.8 Lauryl dimethyl amine oxide 0.6 Tribromosalicylanilide 1.0Resin A 3.0 Water Balance 1 Coco corresponds to the mixture of alkylsderived from a middle cut of coconut oil, that is, 1% C10, 05% C12, 27%C11, and 7% C10.

When the foregoing composition is formulated with a radioactive (C-14tagged) tribromosalicylanilide and the deposition evaluated as describedin Example 1, 1.5 micrograms of antibacterial agent are noted on thegelatin disk. As only 0.5 microgram are deposited in the absence of theAPU resin, use of the APU resin increases deposit by 200%.

EXAMPLE 9 Substitution of 1% of trichlorocarbanilide for thetribromosalicylanilide in the composition of Example 8 yieldssubstantialy similar results.

1 5 EXAMPLE A lotion shampoo composition exhibiting effectivenessagainst P. ovale follows.

Percent by weight Triethanolamine lauryl sulfate 12.5

When the foregoing shampoo having a pH of 8.8 is formulated withradioactive 5,7-diiodo-8-hydroxyquinoline (I-125) and the depositionevaluated using the procedure of Example 5, the APU resin results in a220% increase in the deposition of the antimicrobial agent. Improveddeposition is also obtained when the pH of the composition is 7.8.

When the concentration of 5,7-diiodo-8-hydroxyquinoline is reduced to 1%in the composition of Example 10, APU resin achieves a 133% increase indeposition of that agent.

EXAMPLE 11 The following composition is an improved shampoo composition.

Percent by weight Triethanolamine lauryl sulfate 21.0 Coconutmonoethanolamide 5.0 Triethanolamine 0.7 Sodium chloride 0.8 Methylcellulose 0.9 Ethanol 7.0 Resin A 3.0 Fluorescent agent 1.0 WaterBalance When the foregoing composition is formulated with thefluorescent agents listed in Table 'III and a 1.25% concentrationthereof is used to contact a 1" x 1'' W001 swatch for five minutes, thefluorescent values in Table III are obtained on the wool swatch after itis rinsed with five consecutive 10-milliliter portions of Water and airdried.

The foregoing results show that APU resins improve the brighteningeffectiveness of fluorescent agents of the anionic type (stilbenedisulfonate), nonionic (oxazole) and the cationic type (pyrazoline). Theimprovement noted in fluorescence varies from 7% to 200%.

16 EXAMPLE 12 The following composition is an improved conditioningshampoo.

Percent by weight C to C alkyl 1 amidopropyl dimethyl betaine 16.0

Triethanolamine lauryl sulfate 4.0 Lauryl dimethyl amine oxide 0.5Polyoxypropylene-polyoxyethylene block copolymer having a hydrophobicmolecular weight of 1,750 and containing 20% by weight ofpolyoxyethylene 5.0 Condensation product of 1:1 mixture of ethyleneoxide and propylene oxide on butanol (mol. wt. 4,000) 2.0 Resin A q.s.Ethanol 1.9

Protein q.s. Water, perfume Balance 1 Alkyl group corresponds to themixture of alkyls obtained from middle cut of coconut oil.

2 Wilson Protein WSP-X250 obtained by enzymatic hydrolysls of collagenand having an average molecular weight of about 1,000.

The effectiveness of the aminopolyureylene resin in improving theconditioning properties of the protein is shown by the followingprocedure. A bleached hair tress about 2.5 inches (weight 0.55 gram) isplaced in contact with 55 grams of the shampoo composition of Example 12and the contact is maintained for minutes. The hair tress is thenremoved from the shampoo, subjected to five consecutive rinses withmilliliters of deionized water each time, air dried, and analyzedspectrophotometrically for hydroxyproline. (Hydroxyproline is an aminoacid found in hydrolyzed protein, but not in hair.) The protein andaminopolyureylene resin are soluble in the shampoo composition having apH of 7.5 and the test results for the composition are set forth inTable IV.

TABLE IV.-PERCENT BY WEIGHT Protein Protein Resin A deposited 1Hydroxyproline content expressed as protein. The foregoing tabulationshows that aminopolyureylene resin improves the deposition ofwater-soluble protein onto hair and thereby achieves improvedconditioning eifects.

are substituted for the resin in the composition of Example 12,substantially similar results are obtained.

17 Other compositions exhibiting improved effectiveness because of thepresence of an aminopolyureylene resin therein follow:

EXAMPLE 13 A heavy-duty liquid detergent composition having improvedresistance to color fading because of ultraviolet light follows:

Percent by weight 2,2'-hydroxy-4,4'-dimethoxybenzophenone may besubstituted for the benzophenone in the composition of Example 13 withsubstantially similar improved efiects.

EXAMPLE 14 A built particulate laundry detergent composition exhibitingimproved antibacterial eifectiveness has the following composition:

Percent by Weight Sodium tridecylbenzene sulfonate 17.5 Sodiumtripolyphosphate 40.0 Sodium silicate (1Na O:2.35SiO- 7.0 Sodium sulfate23.1 Tribromosalicylanilide 0.4 Resin A 3.0 Sodiumcarboxymethylcellulose 0.5 Water 8.5

Fabrics laundered in the foregoing composition exhibit improvedantimicrobial efiectiveness.

EXAMPLE 15 A detergent bar composition exhibiting improved resistance tocopper discoloration has the following composition.

Percent by weight Sodium N lauryl B iminodipropionate 8.75 Sodium C to Calkane sulfonate 24.25 Sodium tallow soap 26.40 Sodium tridecylbenzenesulfonate 7.30 Syrupy phosphoric acid (85%) 7.30 Stearic acid 3.60Benzotriazole 0.5 Resin A 4.0 Water Balance Ethylene thiourea may besubstituted for benzotriazole in the composition of Example 15 withsubstantially similar results.

While the improved properties appear to be due primarily to enhanceddeposition and/or retention of both water-soluble and water-insolublematerials due to the presence of the aminopolyureylene resin in thecompositions, the actual mechanism is not completely understood.Accordingly, applicant does not wish to be bound by any particularscientific theory or explanation.

While compositions containing APU resin and an active material may beprepared by admixing resin and active material in any suitable manner,in the preparation of detergent containing compositions, improvedefiects are obtained when the resin and active material are premixedbefore admixing with the detergent component.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that similar results may be obtained when theaminopolyureylene resin is used in combination with a wide 'variety of'watersoluble and water-insoluble substances in addition to thosespecifically described.

What is claimed is:

1. A detergent composition consisting essentially of from 2% to 99% byweight of a water-soluble organic detergent selected from the groupconsisting of anionic, nonionic, amphoteric, zwitterionic, polarnonionic, and cationic detergents; from .05 to 5% by weight of anaminopolyureylene resin having a molecular weight in the range of 300 to100,000 and having the following repeating unit:

-E(CH (X) (CH NHC(Y)NHJ- wherein X is NH, N-C to C alkyl,

/CH:CH2 CH: CHI N N, N N

Y is O or S and n is 2 or 3; and from -05 to 5% by weight of an activematerial selected from the group consisting of Water-insoluble,particulate, ultramarine blue, a tarnish inhibitor selected from thegroup consisting of benzotriazole and ethylenethiourea, and askin-treating compound selected from the group consisting ofwater-soluble polypeptides having a molecular weight of to 20,000 whichare derived by hydrolyzing a boneor skin-derived collagen protein andpolyethylene oxides having a molecular weight in the range of 500,000 to4,000,000, the Weight ratio of resin to active material being effectiveto improve the properties of the active material and being selected fromthe range of 1:1 to 20: 1.

2. A detergent composition in accordance with claim 1 wherein saidactive material is said ultramarine blue.

3. A detergent composition in accordance with claim 1 wherein saidactive material is said tarnish inhibitor.

4. A detergent composition in accordance with claim 1 wherein saidactive material is said skin-treating agent.

5. A detergent composition in accordance with claim 1 wherein said resinhas an average molecular weight in the range of 1,000 to 20,000 and insaid repeating unit YisOandnis3.

6. A detergent composition in accordance with claim 5 wherein said skintreating agent is said water-soluble polypeptide.

7. A detergent composition in accordance with claim 5 wherein said skintreating agent is said polyethylene oxide.

References Cited UNITED STATES PATENTS 3,156,672 11/1964 Van der Kerk eta1. 26077.5 3,240,664 3/ 1966 Earle 162164 3,311,594 3/1967 Earle260-77.5 3,489,686 1/ 1970 Parran 252-406 HERBERT B. GUYNN, PrimaryExaminer P. E. WILLIS, Assistant Examiner U.S. Cl. X.R.

